US5545703A - Electroconductive polymers from unsaturated polymerizable TTF, TCNQ and DCQDI monomers - Google Patents

Electroconductive polymers from unsaturated polymerizable TTF, TCNQ and DCQDI monomers Download PDF

Info

Publication number
US5545703A
US5545703A US08/332,980 US33298094A US5545703A US 5545703 A US5545703 A US 5545703A US 33298094 A US33298094 A US 33298094A US 5545703 A US5545703 A US 5545703A
Authority
US
United States
Prior art keywords
ttf
tcnq
monomers
propenyl
copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US08/332,980
Inventor
Nicholas T. Castellucci
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northrop Grumman Corp
Original Assignee
Northrop Grumman Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northrop Grumman Corp filed Critical Northrop Grumman Corp
Priority to US08/332,980 priority Critical patent/US5545703A/en
Assigned to NORTHROP GRUMMAN CORPORATION, A DELAWARE CORPORATION reassignment NORTHROP GRUMMAN CORPORATION, A DELAWARE CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CASTELLUCCI, NICHOLAS T.
Priority to US08/678,732 priority patent/US5834619A/en
Application granted granted Critical
Publication of US5545703A publication Critical patent/US5545703A/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F228/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a heterocyclic ring containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C261/00—Derivatives of cyanic acid
    • C07C261/04—Cyanamides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/42—Nitriles
    • C08F20/50—Nitriles containing four or more carbon atoms

Definitions

  • the present invention relates to the preparation of novel flexible thermoplastic polymers which are inherently electroconductive, rather than being doped to impart electroconductive properties thereto, and to novel unsaturated monomers of TTF (tetrathiafulvalene), TCNQ (tetracyanoquinodimethane) and DCQDI (dicyanoquinon diimine) which are polymerizable to form homopolymer blends or copolymers having such properties.
  • TTF tetrathiafulvalene
  • TCNQ tetracyanoquinodimethane
  • DCQDI dicyanoquinon diimine
  • TTF tetrathiafulvalene
  • TCNQ tetracyanoquinomethane
  • TTF tetrathiafulvalene
  • TCNQ tetracyanoquinomethane
  • the present invention relates to the discovery of novel polymerizable derivatives of tetrathiafulvalenes (TTF), tetracyanoquinodimethanes (TCNQ) and dicyanoquinodiimines (DCQDI), and to the homo- or co-polymerization of such derivatives to form polymers or polymer blends having excellent inherent electroconductivity properties which are stable and resistant to degradation even at the elevated temperatures encountered during use as electrical materials on advanced aircraft.
  • TTF tetrathiafulvalenes
  • TCNQ tetracyanoquinodimethanes
  • DCQDI dicyanoquinodiimines
  • the present polymerizable derivatives of TTF donor monomers include, in addition to the known 2- or ⁇ -vinyl tetrathiafulvalene, the 2- or ⁇ -acetylene TTF and the 2- or ⁇ -propenyl TTF, and the corresponding bis derivatives, having an acetylene, vinyl or propenyl substituent at the 2- or ⁇ -position of both heterocyclic rings.
  • the present polymerizable derivatives of DCQDI and TCNQ acceptor monomers include the 2-acetylene, 2-vinyl and 2-propenyl derivatives of 7,8-dicyanoquinodiimine and of 7,7,8,8-tetracyanoquinodimethane, and the 2,5-divinyl and 2,5-dipropenyl derivatives of the 7,8-dicyanoquinodiimines and of the 7,7,8,8-tetra-cyanoquinodimethanes.
  • the present polymers include thermoplastic homopolymers and copolymers of said aforementioned polymerizable TTF and TCNQ and DCQDI monomers in which polymerization occurs through the unsaturated radicals. Since the homopolymers of either of said monomers do not contain both the electron donor and the electron acceptor moiety, charge-transfer and pseudo salt-formation cannot occur and the homopolymers are not electroconductive. However, blends of homopolymers of the TTF donor monomer, the TCNQ monomer and/or the DCQDI monomer inter-react ionically to produce charge transfer pseudo salt adducts having strong stable electroconductivity.
  • Copolymers of the present electron-donor and electron-acceptor monomers in which copolymerization occurs through the unsaturated radicals of the donor acceptor monomers, are thermoplastic copolymers having inherent strong, stable electroconductivity since the electron-donor and electron-acceptor moieties are connected to the linear or spiral polymer backbone in close proximity to each other to permit charge transfer and pseudo salt formation to occur along the polymer chain.
  • Tetracyanoquinodimethane is reacted with n-butyl lithium to introduce lithium into the alpha or 2-position of the ring, followed by reaction with N,N-dimethylformamide to replace the lithium group with an aldehyde group.
  • the TCNQ aldehyde is then converted to 2-ethenyl-TCNQ by a Wittig reaction with methyl triphenyl phosphonium bromide and n-butyl lithium, as illustrated by the following reaction sequence: ##STR1##
  • the formed ethenyl- or vinyl-tetracyanoquinodimethane can be homopolymerized by conventional free radical means, using an azo, peroxide, ultraviolet or cationic catalyst in a nitrogen atmosphere to form a solid polymer which does not have electroconductive properties but which can be blended with an electron donor polymer, such as a homopolymer of an ⁇ -unsaturated tetrathiafulvalene, to produce a polymer blend charge-transfer adduct having excellent electroconductive properties.
  • electroconductive copolymers of the 2-unsaturated tetracyanoquinodimethane and the 2- or ⁇ -unsaturated tetrathiafulvalene, and/or the 2- or ⁇ -unsaturated dicyanoquinondiimine can be produced by conventional free radical polymerization, using an azo, peroxide, ultraviolet or cationic catalyst and a nitrogen atmosphere.
  • the copolymerization appears to result in the formation of flexible bridging methylene groups which position the donor moieties of the TTF component in close proximity to the acceptor moieties of the TCNQ and/or DCQDI component for favorable ⁇ -orbital overlap and electron transfer.
  • the following reaction sequence is illustrative: ##STR2##
  • 2,4-dihydroxy benzoic acid is heated in a water ethanol solvent in the presence of a rhodium on aluminum catalyst in a hydrogen atmosphere to produce 2-carboxy quinone.
  • the 2-carboxy quinone is then reacted with 1-propenyl acetate in the presence of a palladium catalyst, Pd(PPh 3 ) 4 , to form 2-(1-propenyl) quinone.
  • the 2-propenyl quinone is then reacted with dicyanomethane and aqueous bromine oxide to form 2-(1-propenyl) tetracyanoquinodimethane.
  • the formed 2-(1-propenyl) TCNQ, or 2-allyl TCNQ is homopolymerizable and copolymerizable in the same manner as the 2-vinyl TCNQ of Example 1.
  • Tetrathiafulvalene is lithiated in the 2-position by reaction with n-butyl lithium in tetrahydrofuran solvent at -80° C. (dry ice). The 2-lithium tetrathiafulvalene is then reacted with 3-bromo-1-propene in ether at -80° C. (dry ice) to form 2-(1-propenyl) TTF.
  • the 2-(1-propenyl) TTF, or 2-allyl TTF is homopolymerizable by free radical polymerization in the presence of an azo or peroxide catalyst in a nitrogen atmosphere.
  • the 2-(1-propenyl) TTF homopolymer of Example 3 can be blended in various relative proportions, including 1:1, with the 2-ethenyl (vinyl) TCNQ homopolymer of Example 1 or with the 2-(1-propenyl) TCNQ polymer (allyl) of Example 2, to form polymer blends having excellent electroconductivity properties.
  • the monomer of TTF (Example 3) can be copolymerized with the TCNQ and DCQDI monomers of Example 1 and/or Example 2 to form copolymers having excellent inherent electroconductivity.
  • Example 4 illustrates the preparation of 2-allyl (2-propenyl) tetracyanoquinodimethane from 2-allyl-1,4-cyclohexanedione.
  • Step I The solid residue from Step I was mixed with 1000 mls of 10% potassium hydroxide solution and stirred for 48 hours at room temperature. The reaction mixture was then treated with concentrated hydrochloric acid (125 mls) added over a period of 30 minutes. The solution was stirred vigorously for 24 hours at ambient temperature.
  • a 2-liter, 3-necked flask was thoroughly dried and fitted with a liquid dropping funnel, nitrogen inlet and rubber septum.
  • a magnetic stirring bar was placed in the flask.
  • the flask was then charged with tetrathiafulvalene (13.0 g, 0.064 moles).
  • the system was evacuated and back filled with nitrogen.
  • Tetrahydrofuran 500 mls was added and the solution stirred until the tetrathiafulvalene dissolved.
  • the solution was cooled to -78° C. using a dry ice/acetone bath.
  • a solution of lithium dimethyamide (3.5 g, 0.064 moles) in 250 mls of tetrahydrofuran was added to the dropping funnel.
  • reaction mixture was stirred at 78° C. for another hour, then allowed to slowly warm to room temperature. An orange-red solution resulted. The solvent was removed under vacuum.
  • the residue was dissolved in two liters of ethyl ether and 500 mls of water.
  • the aqueous phase was washed with 2 ⁇ 200 mls of ethyl ether.
  • the organic phases were combined and dried over anhydrous magnesium sulfate.
  • the solvent was then removed under vacuum, leaving a red-brown solid and dark liquid.
  • the residue was added to 500 mls of hexane and shaken. The orange supernatant was decanted. The remaining solid was isolated and analyzed to confirm that it was TTF.
  • the hexane solution was poured onto a 6" silica gel column.
  • the column was repeatedly washed with hexane until the washing were almost colorless.
  • the column was then washed with methylene chloride, which removed most of the material on the column.
  • the solution was evaporated to dryness leaving an orange oil. Based on the C-13 nmr, the product comprises a mixture of 2,6-diallyl and 2,7-diallyltetrathia-fulvalene.
  • DiallylTTF (lot 207-C, ⁇ 0.29 g) was dissolved in 20 mls of dry tetrahydrofuran. The solution was treated with ⁇ 50mg of AIBN. The solution was photolyzed with a medium pressure mercury lamp (254 nm) at room temperature and under an atmosphere of nitrogen. Slowly the color changed to orange. After 12 hours the reaction was stopped. The solution was evaporated to dryness leaving a light-brown oily residue. Unlike the starting material, the product was only sparingly soluble in chloroform. ##
  • 2-AllyltetrahydroTCNQ ( ⁇ 1.0 g) was dissolved in 20 mls of tetrahydrofuran forming an orange solution.
  • the solution was treated with ⁇ 50mg of AIBN, then photolyzed with a medium pressure mercury lamp (254 nm) at room temperature and under an atmosphere of nitrogen for 18 hours. No significant change was observed in the color of the solution.
  • the volatiles were removed under vacuo at 50° C. A waxy, orange solid was isolated.
  • the present ethylenically-unsaturated monomers can be copolymerized with other ethylenically-unsaturated monomers, such as vinyl monomers, to form a variety of different copolymers having desirable properties imparted by the other monomoers and having electroconductivity imparted by the present TTF, TCNQ and DCQDI monomers.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Polymeric compositions having inherent electroconductive properties and unsaturated electron-donor and electron-receptor polymerizable monomers for producing such compositions in the form of blends of homopolymers of such monomers or as copolymers of such monomers.

Description

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the preparation of novel flexible thermoplastic polymers which are inherently electroconductive, rather than being doped to impart electroconductive properties thereto, and to novel unsaturated monomers of TTF (tetrathiafulvalene), TCNQ (tetracyanoquinodimethane) and DCQDI (dicyanoquinon diimine) which are polymerizable to form homopolymer blends or copolymers having such properties.
2. Discussion of the Art
The pseudosalt of TTF (tetrathiafulvalene) and TCNQ (tetracyanoquinomethane) is well known as the most (electrically-conductive) organic compound. Its conductivity is metallic-like in that it increases as the temperature of the pseudosalt decreases. The pseudosalt is a charge-transfer complex wherein the donor moiety is the TTF and the electron acceptor moiety is the TCNQ. Reference is made to U.S. Pat. No. 4,036,648.
It is known to impart electroconductive properties to an existing polymer by doping or reacting it with TTF and/or TCNQ, and reference is made to U.S. Pat. Nos. 4,312,992; 4,543,319 and 4,769,177. Polymers produced as disclosed in these patents do not comprise the TTF compound or the TCNQ compound as integral components of the polymer backbone and therefore are less stable, have less temperature-resistant conductivity properties and have lower electroconductivity than the novel polymers of the present invention.
The only known unsaturated derivative of either TTF, TCNQ or DCQDI is vinyl TTF which is disclosed in aforementioned U.S. Pat. No. 4,312,992. However, said patent does not disclose that vinyl TTF is polymerizable, and only discloses coupling the charge-transfer compounds of TTF and TCNQ to existing polymers to produce electroconductive polymers.
SUMMARY OF THE INVENTION
The present invention relates to the discovery of novel polymerizable derivatives of tetrathiafulvalenes (TTF), tetracyanoquinodimethanes (TCNQ) and dicyanoquinodiimines (DCQDI), and to the homo- or co-polymerization of such derivatives to form polymers or polymer blends having excellent inherent electroconductivity properties which are stable and resistant to degradation even at the elevated temperatures encountered during use as electrical materials on advanced aircraft.
The present polymerizable derivatives of TTF donor monomers include, in addition to the known 2- or α-vinyl tetrathiafulvalene, the 2- or α-acetylene TTF and the 2- or α-propenyl TTF, and the corresponding bis derivatives, having an acetylene, vinyl or propenyl substituent at the 2- or α-position of both heterocyclic rings.
The present polymerizable derivatives of DCQDI and TCNQ acceptor monomers include the 2-acetylene, 2-vinyl and 2-propenyl derivatives of 7,8-dicyanoquinodiimine and of 7,7,8,8-tetracyanoquinodimethane, and the 2,5-divinyl and 2,5-dipropenyl derivatives of the 7,8-dicyanoquinodiimines and of the 7,7,8,8-tetra-cyanoquinodimethanes.
The present polymers include thermoplastic homopolymers and copolymers of said aforementioned polymerizable TTF and TCNQ and DCQDI monomers in which polymerization occurs through the unsaturated radicals. Since the homopolymers of either of said monomers do not contain both the electron donor and the electron acceptor moiety, charge-transfer and pseudo salt-formation cannot occur and the homopolymers are not electroconductive. However, blends of homopolymers of the TTF donor monomer, the TCNQ monomer and/or the DCQDI monomer inter-react ionically to produce charge transfer pseudo salt adducts having strong stable electroconductivity.
Copolymers of the present electron-donor and electron-acceptor monomers, in which copolymerization occurs through the unsaturated radicals of the donor acceptor monomers, are thermoplastic copolymers having inherent strong, stable electroconductivity since the electron-donor and electron-acceptor moieties are connected to the linear or spiral polymer backbone in close proximity to each other to permit charge transfer and pseudo salt formation to occur along the polymer chain.
The following examples illustrate the formation of the monomers of the present invention.
EXAMPLE 1 Preparation of Ethenyl-TCNQ
Tetracyanoquinodimethane is reacted with n-butyl lithium to introduce lithium into the alpha or 2-position of the ring, followed by reaction with N,N-dimethylformamide to replace the lithium group with an aldehyde group. The TCNQ aldehyde is then converted to 2-ethenyl-TCNQ by a Wittig reaction with methyl triphenyl phosphonium bromide and n-butyl lithium, as illustrated by the following reaction sequence: ##STR1##
The formed ethenyl- or vinyl-tetracyanoquinodimethane can be homopolymerized by conventional free radical means, using an azo, peroxide, ultraviolet or cationic catalyst in a nitrogen atmosphere to form a solid polymer which does not have electroconductive properties but which can be blended with an electron donor polymer, such as a homopolymer of an α-unsaturated tetrathiafulvalene, to produce a polymer blend charge-transfer adduct having excellent electroconductive properties.
Alternatively, electroconductive copolymers of the 2-unsaturated tetracyanoquinodimethane and the 2- or α-unsaturated tetrathiafulvalene, and/or the 2- or α-unsaturated dicyanoquinondiimine, can be produced by conventional free radical polymerization, using an azo, peroxide, ultraviolet or cationic catalyst and a nitrogen atmosphere. The copolymerization appears to result in the formation of flexible bridging methylene groups which position the donor moieties of the TTF component in close proximity to the acceptor moieties of the TCNQ and/or DCQDI component for favorable π-orbital overlap and electron transfer. The following reaction sequence is illustrative: ##STR2##
EXAMPLE 2 Preparation of 2-(1-propenyl) TCNQ
2,4-dihydroxy benzoic acid is heated in a water ethanol solvent in the presence of a rhodium on aluminum catalyst in a hydrogen atmosphere to produce 2-carboxy quinone. The 2-carboxy quinone is then reacted with 1-propenyl acetate in the presence of a palladium catalyst, Pd(PPh3)4, to form 2-(1-propenyl) quinone. The 2-propenyl quinone is then reacted with dicyanomethane and aqueous bromine oxide to form 2-(1-propenyl) tetracyanoquinodimethane.
The formed 2-(1-propenyl) TCNQ, or 2-allyl TCNQ, is homopolymerizable and copolymerizable in the same manner as the 2-vinyl TCNQ of Example 1.
EXAMPLE 3 Preparation of 2-(1-propenyl) TTF
Tetrathiafulvalene is lithiated in the 2-position by reaction with n-butyl lithium in tetrahydrofuran solvent at -80° C. (dry ice). The 2-lithium tetrathiafulvalene is then reacted with 3-bromo-1-propene in ether at -80° C. (dry ice) to form 2-(1-propenyl) TTF.
The 2-(1-propenyl) TTF, or 2-allyl TTF, is homopolymerizable by free radical polymerization in the presence of an azo or peroxide catalyst in a nitrogen atmosphere.
The 2-(1-propenyl) TTF homopolymer of Example 3 can be blended in various relative proportions, including 1:1, with the 2-ethenyl (vinyl) TCNQ homopolymer of Example 1 or with the 2-(1-propenyl) TCNQ polymer (allyl) of Example 2, to form polymer blends having excellent electroconductivity properties.
Also, the monomer of TTF (Example 3) can be copolymerized with the TCNQ and DCQDI monomers of Example 1 and/or Example 2 to form copolymers having excellent inherent electroconductivity.
The following Example 4 illustrates the preparation of 2-allyl (2-propenyl) tetracyanoquinodimethane from 2-allyl-1,4-cyclohexanedione.
EXAMPLE 4 Preparation of 2-Allyltetracyanoquinodimethane ##STR3## Compound A - 1,4-Dioxaspiro[4.5]decan-8-one Compound B - 8-Pyrrolidyl-1,4-dioxaspiro[4.5]dec-7-ene
Compound C - 2-Allyl-1,4-cyclohexanedione
Compound D - 2-Allyl-2,3,5,6-tetrahydrotetracyanoquinodimethane
Compound E - 2-Allyltetracyanoquinodimethane
Step I Preparation of the intermediate ammonium salt
A 2-liter, 3-necked flask was equipped with a mechanical stirrer and charged with Compound B, 8-pyrrolidyl-1,4-dioxaspiro[4,5]dec-7-ene (125 g, 0.60 moles). The liquid was then treated with acetonitrile (500 mls, dried over molecular sieves) and allyl bromide (80 g, 0.65 moles). The reaction mixture was stirred and mildly refluxed under nitrogen for three, eight hour periods (not refluxed overnight). Upon cooling, product crystallized. While heating with a water bath, all the solvent was removed under vacuum.
Step II Preparation of 2-allyl-1,4-cyclohexanedione (Compound C)
The solid residue from Step I was mixed with 1000 mls of 10% potassium hydroxide solution and stirred for 48 hours at room temperature. The reaction mixture was then treated with concentrated hydrochloric acid (125 mls) added over a period of 30 minutes. The solution was stirred vigorously for 24 hours at ambient temperature.
The solution was extracted with 4×150 mls portions of diethyl ether. The ether extract was dried over anhydrous magnesium sulfate, then filtered. The filtrate was evaporated to an oil. The residue was transferred to a 200 ml round-bottom flask and any remaining material was washed out using a small amount of ethyl ether. The product was distilled under vacuum as Compound C.
Yield--76 g (75%)
Boiling Point--95°-100° C. (1.0-1.5 mm)
Lot number--1358-P
Carbon--13 nmr--enclosed
Reaction III Preparation of 2-Allyl-2,3,5,6-tetrahydro-tetracyanoquinodimethane (Compound D)
A test run was conducted on the preparation of compound D using impure 2-allyl-1,4-cyclohexanedione. Ten grams of allylcyclohexanedione was mixed with 10 g of malononitrile. The mixture was warmed to 90° C., producing a melt. The mixture was kept at 90° C. for ten minutes, then treated with 50 mls of water containing 50mg of beta-alanine, previously warmed to 90° C. The mixture was stirred vigorously. Slowly, an off-white solid began to form. The reaction mixture was cooled to room temperature and the solid filtered. The product was washed thoroughly with water, then allowed to air dry. The off-white powder was sent for nmr analysis. The nmr is consistent with the formation of Compound D which, under bromination, forms Compound E.
EXAMPLE 5 Preparation of 2-Allyltetrathiafulvalene
Glassware was dried at 120° C. for two hours. Tetrahydrofuran was freshly distilled from sodium/benzophenone. Allyl bromide was dried over 4A molecular sieves and filtered through silica gel before use.
A 2-liter, 3-necked flask was thoroughly dried and fitted with a liquid dropping funnel, nitrogen inlet and rubber septum. A magnetic stirring bar was placed in the flask. The flask was then charged with tetrathiafulvalene (13.0 g, 0.064 moles). The system was evacuated and back filled with nitrogen. Tetrahydrofuran (500 mls) was added and the solution stirred until the tetrathiafulvalene dissolved. The solution was cooled to -78° C. using a dry ice/acetone bath. A solution of lithium dimethyamide (3.5 g, 0.064 moles) in 250 mls of tetrahydrofuran was added to the dropping funnel. While stirring, the solution was added dropwise to the reaction mixture over a period of 90 minutes. No visible change was observed. The reaction mixture was allowed to stir for another hour at -78° C., then allyl bromide (9.0 mls) was added, all at once, using a syringe. Again, no visible change was observed.
The reaction mixture was stirred at 78° C. for another hour, then allowed to slowly warm to room temperature. An orange-red solution resulted. The solvent was removed under vacuum.
The residue was dissolved in two liters of ethyl ether and 500 mls of water. The aqueous phase was washed with 2×200 mls of ethyl ether. The organic phases were combined and dried over anhydrous magnesium sulfate. The solvent was then removed under vacuum, leaving a red-brown solid and dark liquid. The residue was added to 500 mls of hexane and shaken. The orange supernatant was decanted. The remaining solid was isolated and analyzed to confirm that it was TTF.
The hexane solution was poured onto a 6" silica gel column. The column was repeatedly washed with hexane until the washing were almost colorless. The column was then washed with methylene chloride, which removed most of the material on the column. The solution was evaporated to dryness leaving an orange oil. Based on the C-13 nmr, the product comprises a mixture of 2,6-diallyl and 2,7-diallyltetrathia-fulvalene.
EXAMPLE 6 Polymerization of Diallyltetrathiafulvalene
DiallylTTF (lot 207-C, ˜0.29 g) was dissolved in 20 mls of dry tetrahydrofuran. The solution was treated with ˜50mg of AIBN. The solution was photolyzed with a medium pressure mercury lamp (254 nm) at room temperature and under an atmosphere of nitrogen. Slowly the color changed to orange. After 12 hours the reaction was stopped. The solution was evaporated to dryness leaving a light-brown oily residue. Unlike the starting material, the product was only sparingly soluble in chloroform. ##STR4##
EXAMPLE 7 Polymerization of 2-Allylthetrahydrotetracyanoquinodimethane ##STR5##
2-AllyltetrahydroTCNQ (˜1.0 g) was dissolved in 20 mls of tetrahydrofuran forming an orange solution. The solution was treated with ˜50mg of AIBN, then photolyzed with a medium pressure mercury lamp (254 nm) at room temperature and under an atmosphere of nitrogen for 18 hours. No significant change was observed in the color of the solution. The volatiles were removed under vacuo at 50° C. A waxy, orange solid was isolated.
EXAMPLE 8 Preparation of 2-Propenyl-N,N-dicyano-1,4-quinondiimine ##STR6## EXAMPLE 9 Preparation of 2-Ethenyl-N, N-dicyano-1,4-quinondiimine ##STR7##
It will also be apparent to those skilled in the art that the present ethylenically-unsaturated monomers can be copolymerized with other ethylenically-unsaturated monomers, such as vinyl monomers, to form a variety of different copolymers having desirable properties imparted by the other monomoers and having electroconductivity imparted by the present TTF, TCNQ and DCQDI monomers.
It should be understood that the foregoing description is only illustrative of the invention. Various alternatives and modifications can be devised by those skilled in the art without departing from the invention. Accordingly, the present invention is intended to embrace all such alternatives, modifications and variances which fall within the scope of the appended claims.

Claims (5)

What is claimed is:
1. A thermoplastic copolymer having inherent electroconductive properties comprising a copolymer of equimolar amounts of a tetrathiafulvalene monomer having the formula: ##STR8## in which R1 is selected from the group consisting of hydrogen, CH2 ═CH--, and CH2 ═CH--CH2 --, R2 is selected from the group consisting of CH2 ═CH--, and CH2 ═CH--CH2 --, and a polycyano-quinodimethane monomer having the formula: ##STR9## in which R is selected from the group consisting of CH≡C--, CH2 ═CH--, and CH2 ═CH--CH2 --, R1 is R or H, and R2 is NC-- or H.
2. A thermoplastic copolymer having inherent electroconductive properties comprising a copolymer of equimolar amounts of a tetrathiafulvalene monomer having the formula: ##STR10## in which R is selected from the group consisting of hydrogen, CH2 ═CH--, and CH2 ═CH--CH2 --, R2 is selected from the group consisting of CH2 ═CH--, and CH2 ═CH--CH2 --, and a dicyanoquinondiimine monomer having the formula: ##STR11## in which R is selected from the group consisting of CH2 ═CH--, and CH2 ═CH--CH2.
3. A copolymer according to claim 1 comprising a copolymer of equimolar amounts of 2-ethenyl tetracyanoquinodimethane and 2-ethenyl tetrathiafulvalene.
4. A copolymer according to claim 1 comprising a copolymer of equimolar amounts of 2-1(1-propenyl)tetracyanoquinodimethane and 2-(1-propenyl tetrathiafulvalene.
5. A copolymer according to claim 2 comprising a copolymer of equimolar amounts of 2-propenyl-N,N-dicyano-1,4-quinondiimine and 2-(1-propenyl) tetrathiafulvalene.
US08/332,980 1994-11-01 1994-11-01 Electroconductive polymers from unsaturated polymerizable TTF, TCNQ and DCQDI monomers Expired - Fee Related US5545703A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US08/332,980 US5545703A (en) 1994-11-01 1994-11-01 Electroconductive polymers from unsaturated polymerizable TTF, TCNQ and DCQDI monomers
US08/678,732 US5834619A (en) 1994-11-01 1996-07-11 Unsaturated polymerizable cyanoquinodimethane monomers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US08/332,980 US5545703A (en) 1994-11-01 1994-11-01 Electroconductive polymers from unsaturated polymerizable TTF, TCNQ and DCQDI monomers

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US08/678,732 Division US5834619A (en) 1994-11-01 1996-07-11 Unsaturated polymerizable cyanoquinodimethane monomers

Publications (1)

Publication Number Publication Date
US5545703A true US5545703A (en) 1996-08-13

Family

ID=23300730

Family Applications (2)

Application Number Title Priority Date Filing Date
US08/332,980 Expired - Fee Related US5545703A (en) 1994-11-01 1994-11-01 Electroconductive polymers from unsaturated polymerizable TTF, TCNQ and DCQDI monomers
US08/678,732 Expired - Fee Related US5834619A (en) 1994-11-01 1996-07-11 Unsaturated polymerizable cyanoquinodimethane monomers

Family Applications After (1)

Application Number Title Priority Date Filing Date
US08/678,732 Expired - Fee Related US5834619A (en) 1994-11-01 1996-07-11 Unsaturated polymerizable cyanoquinodimethane monomers

Country Status (1)

Country Link
US (2) US5545703A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5871670A (en) * 1994-09-21 1999-02-16 Ciba Specialty Chemicals Corporation Electroconductive composition
CN107531936A (en) * 2015-02-10 2018-01-02 美利肯公司 Thermoplastic polymer composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4036648A (en) * 1975-06-30 1977-07-19 International Business Machines Corporation Highly conductive printing medium containing a halogenated hydrocarbon photoactivator and a tetrathiafulvalene or a related compound thereof
US4312992A (en) * 1976-12-03 1982-01-26 International Business Machines Corporation Substituted heterofulvalenes
US4543319A (en) * 1982-12-30 1985-09-24 International Business Machines Corporation Polystyrene-tetrathiafulvalene polymers as deep-ultraviolet mask material
US4769177A (en) * 1980-02-16 1988-09-06 Bayer Aktiengesellschaft Electrically conductive and antistatic moulding compositions

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62207249A (en) * 1986-03-06 1987-09-11 Agency Of Ind Science & Technol Electron acceptor containing long-chain hydrocarbon group and electric charge transfer complex compound thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4036648A (en) * 1975-06-30 1977-07-19 International Business Machines Corporation Highly conductive printing medium containing a halogenated hydrocarbon photoactivator and a tetrathiafulvalene or a related compound thereof
US4312992A (en) * 1976-12-03 1982-01-26 International Business Machines Corporation Substituted heterofulvalenes
US4769177A (en) * 1980-02-16 1988-09-06 Bayer Aktiengesellschaft Electrically conductive and antistatic moulding compositions
US4543319A (en) * 1982-12-30 1985-09-24 International Business Machines Corporation Polystyrene-tetrathiafulvalene polymers as deep-ultraviolet mask material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Nisshin Electric Co. Ltd., Chemical Abstracts, vol. 103, p. 84, #143543k, 1985.
Nisshin Electric Co. Ltd., Chemical Abstracts, vol. 103, p. 84, 143543k, 1985. *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5871670A (en) * 1994-09-21 1999-02-16 Ciba Specialty Chemicals Corporation Electroconductive composition
CN107531936A (en) * 2015-02-10 2018-01-02 美利肯公司 Thermoplastic polymer composition
CN107531936B (en) * 2015-02-10 2019-05-14 美利肯公司 Thermoplastic polymer composition

Also Published As

Publication number Publication date
US5834619A (en) 1998-11-10

Similar Documents

Publication Publication Date Title
Yamaguchi et al. Toward new materials for organic electroluminescent devices: synthesis, structures, and properties of a series of 2, 5‐diaryl‐3, 4‐diphenylsiloles
Hall Jr et al. Electron-deficient trisubstituted olefins. A new class of reactive comonomers
Van Pham et al. A convenient synthesis of 2, 5-thienylene oligomers; some of their spectroscopic and electrochemical properties
Sanda et al. Radical polymerization behavior of 1, 1-disubstituted 2-vinylcyclopropanes
US4508882A (en) Benzotriazole compound and homopolymer or copolymers thereof
US6051679A (en) Self-acid-doped highly conducting polythiophenes
WO1997039082A1 (en) Conjugated polymers with hetero spiro-atoms and their use as electroluminescent materials
CN113563314A (en) Phenanthroimidazole derivative and preparation method and application thereof
TW200540195A (en) Polymers having pendant triarylmethane groups and electronic devices made with such polymers
US5545703A (en) Electroconductive polymers from unsaturated polymerizable TTF, TCNQ and DCQDI monomers
US5840935A (en) Unsaturated polymerizable TTF, TCNQ and DCQDI monomers
JP2001335622A (en) Novel compound, and production method and use thereof
Barbarella et al. Polyhydroxyl oligothiophenes. I. Regioselective synthesis of 3, 4′-and 3, 3′-di (2-hydroxyethyl)-2, 2′-bithiophene via palladium catalyzed coupling of thienylstannanes with thienylbromides.
JP2862753B2 (en) Thiophene-silole copolymer and method for producing the same
Della-Casa et al. Monomers of 3-alkyl-substituted thiophene: synthetic routes for the functionalization with non-linear optical chromophores
US4652399A (en) Novel polyacrylic esters bearing pendant macrocyclic ethers and electrically conducting compositions comprised thereof
Geißler et al. Poly {arylene‐alt‐[bis (1‐methylpyrrolylene)]} s, 1. Synthesis and electrochemical polymerization of terarenes
US5314976A (en) Photo-responsive conductive polymers and the processes of making the same
Itoh et al. 7-Chloro-7-phenyl-8, 8-dicyanoquinodimethane. A novel initiator for cationic polymerizations
JPH05262993A (en) Polymer conductor and its production
CA1296129C (en) Polymerization of acrylic derivatives
Itoh et al. Synthesis and polymerization of 7, 7‐bis (alkoxycarbonyl)‐1, 4‐benzoquinone methides
US5412105A (en) Thiophene-silole copolymer and its method of manufacture
US3294763A (en) Organic compounds and method of making same
Iwatsuki et al. Change in polymerization mode of 7, 7, 8, 8-tetracyanoquinodimethane and 2-chloroethyl vinyl ether upon replacement of solvent

Legal Events

Date Code Title Description
AS Assignment

Owner name: NORTHROP GRUMMAN CORPORATION, A DELAWARE CORPORATI

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CASTELLUCCI, NICHOLAS T.;REEL/FRAME:007211/0700

Effective date: 19941028

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20080813